CN101096274B - Preparation method of aluminum-enriched beta zeolite - Google Patents
Preparation method of aluminum-enriched beta zeolite Download PDFInfo
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- CN101096274B CN101096274B CN2006100905752A CN200610090575A CN101096274B CN 101096274 B CN101096274 B CN 101096274B CN 2006100905752 A CN2006100905752 A CN 2006100905752A CN 200610090575 A CN200610090575 A CN 200610090575A CN 101096274 B CN101096274 B CN 101096274B
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Abstract
The invention discloses a making method of allitic beta-zeolite, which comprises the following steps: making silica-alumina gel through silicon source and aluminium source under hydrolytic reagent; aging at 20-220 deg. c; roasting at 300-1400 deg. c; grinding the gel into silica-alumina source; adding the solution with ammonium tetraethyl cation, ammonium ion, fluorine ion and water; crystallizing; recycling the crystallized product as zeolite.
Description
Technical field
The invention relates to a kind of crystalline silicate prepare zeolite method, more specifically say so about a kind of preparation method of aluminum-enriched beta zeolite.
Background technology
The beta zeolite is (Wadlinger R.L, Kerr G.T, the Rosinski E.J.US3308069) that U.S. Mobile company 1967 adopts classical hydrothermal crystallization method to be synthesized first.This zeolite has unique three-dimensional open-framework, have higher hydrocracking and hydro-isomerization catalytic activity, behind modification or some metal constituent element of load, can be used for refining of petroleum and petrochemical process such as hydrocracking, hydro-isomerization, hydrofining and Hydrodewaxing, diesel oil pour point depression.Said beta zeolite is such synthetic: will contain Na
2O, Al
2O
3, TEAOH, SiO
2Make slurries with the mixture of water, in 75～200 ℃ of crystallizations 3～60 days, the molar ratio of this reaction system was: SiO in autoclave
2/ Al
2O
3=10～200, Na
2O/TEAOH=0.0～0.1, TEAOH/SiO
2=0.1～1.0, H
2O/TEAOH=20～75.The silica alumina ratio of the beta zeolite that the employing aforesaid method obtains is difficult to prepare allitic beta-zeolite all 20～250.
Vaudry etc. (Vaudry F., Renzo F.D., et al., Zeolites, 1997,19:254) the beta zeolite that contains 6 aluminium atoms in the unit cell is defined as the stoichiometry zeolite, corresponding its silica alumina ratio (SiO
2/ Al
2O
3) be 19.3, and then silica alumina ratio is lower than 19.3 β zeolite allitic beta-zeolite (Aluminum-rich β zeolite).
Borade etc. (R.B.Borade and A.Clearfield.Chem.Commun., 1996.625) are by earlier being prepared into the dry powder method of crystallization again with reaction mass, at the silica alumina ratio that feeds intake are to have prepared aluminum-enriched beta zeolite (SiO under 9 the condition
2/ Al
2O
3=9).This reaction system adopts be fuming silica gel, sodium metaaluminate, tetraethyl ammonium hydroxide and deionized water to make raw material, and its mole that feeds intake consists of: 1Na
2O:Al
2O
3: 9SiO
2: 1.6TEAOH:60H
2O was 170 ℃ of following crystallization 2 days.But this method easily produces dephasign such as Gismondine, Analcime.
Zhou Qun etc. (Zhou Qun, Pang Wenqin, Qiu Shilun, monarch Jia Ming .CN1086792,1994) adopt directing agent method to synthesize aluminum-enriched beta zeolite under the very low situation of template TEAOH consumption, and silica alumina ratio scope narrower (silica alumina ratio 8～15) approaches ultrastable Y.This method at first needs to prepare directed agents, then respectively with sodium aluminate, sodium hydroxide, silicon source, aluminium source, deionized water and β guiding agent for zeolite (add directed agents amount account for the synthetic mixture cumulative volume 0.5%～10%) mix, crystallization is 2 days under 413K.In this method, the utilization ratio of silicon is low, roasting back skeleton aluminium instability.
(M.Matsukata such as M.Matsukata, M.Ogura, T.Osaki, E.Kikuchi, A.Mitra.Microporous and Mesoporous Materials48 (2001) 23～29) utilize water vapor auxiliary crystallization method to synthesize aluminum-enriched beta zeolite, minimum silica alumina ratio is 7.Described method adopts aluminium hydroxide, silicon and aluminum source made by tetraethyl silicate and tetraethyl ammonium hydroxide is made template.At first need to form: SiO with sodium hydroxide, tetraethyl ammonium hydroxide solution, aluminium hydroxide and tetraethyl silicate preparation mole
2: xAl
2O
3: TEAOH:0.098Na
2O:33.3H
2O, the gel of (x〉0.033), gel need wear out 24 hours in 15 ℃ before crystallization, then in 60 ℃ of dried overnight, crystallization is carried out in the reactor of inner liner polytetrafluoroethylene 55ml, feed intake minimum that crystallization needs lower temperature 373K and long crystallization time (at least 10 days) during silica alumina ratio 7, product is unformed when in higher temperature 413K crystallization.The template dosage that adopts this method to use is very big and crystallization time is longer, has therefore limited industrialization.
In WO97/33830, containing F first
-Ion and TEA
+Ion is near under the neutral condition, very wide silica alumina ratio scope (SiO
2/ Al
2O
3The beta zeolite that synthesizes pure phase in=12.286～∞).This method is a raw material with tetraethyl silicate and metallic aluminium powder, makes template with tetraethyl ammonium hydroxide, adds hydrofluoric acid simultaneously, gel silica alumina ratio (SiO
2/ Al
2O
3) minimumly reaching 12, the beta zeolite silica alumina ratio of preparation is minimum to reach 14.4, but crystallization time reaches 62 days.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of aluminum-enriched beta zeolite is provided.
Aluminum-enriched beta zeolite preparation method provided by the invention is characterized in that this method contains following step:
(a) silicon source and aluminium source are mixed in the presence of hydrolytic reagent to obtain sial cogelled, said hydrolytic reagent is selected from one or more in the following material: organic acid, mineral acid, organic amine, ammoniacal liquor, Neutral ammonium fluoride;
(b) sial is cogelled through pulverizing as silicon and aluminum source after 20～220 ℃ of aging and 300～1400 ℃ of roastings;
(c) silicon and aluminum source is added in the solution of being made up of tetraethylammonium cation, ammonium radical ion, fluorion and water, forming the mole proportioning is SiO
2/ Al
2O
3=3～20, Na
2O/SiO
2=0～0.01, H
2O/Si
2=1.0～8.0, TEA
+/ SiO
2=0.1～1.0, F
-/ SiO
2=0.1～1.0 reaction mixture;
(d) reaction mixture is being descended crystallization and reclaiming crystallization product in enclosed system.
Among the preparation method provided by the invention, said silicon source is preferably adopted facile hydrolysis, is dissolved in pure organosilicon, as methyl silicate, tetraethyl silicate etc. in the step (a); Said aluminium source is preferably adopted and is soluble in pure aluminium alcoholates salt or inorganic aluminate soluble in water, wherein, and aluminium alcoholates salt such as trimethyl carbinol aluminium, aluminum isopropylate etc., inorganic aluminate such as Tai-Ace S 150, aluminum nitrate, aluminum chloride etc.; Said hydrolytic reagent is selected from Neutral ammonium fluoride, ammoniacal liquor, organic amine, organic acid or mineral acid, and wherein, organic acid is preferably as formic acid, acetate, oxalic acid etc., and mineral acid is preferably as nitric acid, hydrochloric acid etc.
In step (a), can be with water, dehydrated alcohol, anhydrous isopropyl alcohol or their mixture as solvent, for raw materials such as silicon source, aluminium source, hydrolytic reagent and solvent addition sequence, the present invention there is no special requirement, is generally order and adds.The cogelled one-tenth adhesive tape of said sial part is preferably pH=513, becomes 25～80 ℃ of glue temperature, gelation time 0.1～24 hour.
Among the preparation method provided by the invention, step (b) is that the sial of step (a) is cogelled 20 ℃～220 ℃ aging down, pulverizing, 300 ℃～1400 ℃ following calcination process, preferred 12～the 48h of wherein said digestion time, the preferred 20-200 order of particle after the said pulverizing, said calcination process generally continue 1～48h.
Among the preparation method provided by the invention, step (c) is that the cogelled particle of solid-state sial that step (b) is obtained is a silicon and aluminum source, adds tetraethyl ammonium (TEA
+) positively charged ion, F
-The solution that ion and water are formed, homogeneous obtains mixture, and the mol ratio of said mixture system is formed: SiO
2/ Al
2O
3=3～20, Na
2O/SiO
2=0.0～0.025, H
2O/SiO
2=1.0～8.0, TEA
+/ SiO
2=0.1～1.0, F/SiO
2=0.1～1.0.In the said mixture system of step (c), pH preferably is controlled at 5～12, more preferably 6～9, can regulate the content of pH value and fluorion by adding ammoniacal liquor, hydrofluoric acid or Neutral ammonium fluoride.
Among the preparation method provided by the invention, the process of the crystallization process of said reaction mixture and recovery crystallization product is well known to those skilled in the art in the step (d), normally, obtain the beta zeolite through filtration, washing, exsiccant process then with reaction mixture 75 ℃～200 ℃, preferred 135～190 ℃ of reactions 1～30 day under encloses container, autogenous pressure.
The preparation method of the allitic beta-zeolite that the wood invention provides is characterized in that mix, cogelled as silicon source and aluminium source through the solid-state sial of pyroprocessing; In the cogelled preparation of sial, do not introduce template tetraethyl ammonium (TEA
+) positively charged ion, system has lower alkali metal content, just introduces template positively charged ion and F then before crystallization
-Ion.
Preparation method provided by the invention especially goes out aluminum-enriched beta zeolite at feed intake low silica-alumina ratio and water silicon than crystallization under the condition, detects mutually through the XRD thing not contain other crystalline phases; Compare with preparation method in the past, zeolite crystallinity height, yield height, and also crystallization time shortens greatly.
The aluminum-enriched beta zeolite of method preparation provided by the invention does not need through overpickling and ammonium ion exchange, can directly be transformed into Hydrogen beta zeolite through behind the roasting removed template method.
The aluminum-enriched beta zeolite of method preparation provided by the invention, can be used as carrier or catalyzer constituent element, because have more highdensity acid site, thereby have better hydrocracking and hydro-isomerization catalytic activity, behind modification or some metal constituent element of load, can be used for refining of petroleum and petroleum refining processes such as hydrocracking, hydro-isomerization, hydrofining and Hydrodewaxing, diesel oil pour point depression.In addition, can also be used as ion-exchanger and sorbent material, at industrial bavin, the gasoline desulfur of can be used for, perhaps as vehicle exhaust desulfurization, denitrification catalyst, auxiliary agent etc.
Description of drawings
Accompanying drawing 1 is the XRD spectra of standard industry β 30 zeolites.
Accompanying drawing 2 is the XRD spectra of beta zeolite of the preparation of embodiment 1.
Embodiment
Below by embodiment the present invention is further described, but content not thereby limiting the invention.
Embodiment 1～5
Raw material and the proportioning of embodiment 1～5 are shown in Table 1.It is cogelled at first to prepare sial, and the sial of preparation is cogelled at 20 ℃～220 ℃ down aging 12～48h, grind to form then less than 20 order particles, and continuation is handled down at 400 ℃, 500 ℃, 600 ℃, 800 ℃, 1200 ℃ respectively.Control suitable proportioning raw materials, add tetraethyl ammonium hydroxide (TEAOH), water and hydrofluoric acid, even through ultra-sonic dispersion or mechanical stirring, be placed on then and carry out crystallization in the reactor.Crystallization is taken out water cooling after the time that needs, reacted material filtering washing is drying to obtain aluminum-enriched beta zeolite at 120 ℃.Product silica alumina ratio and degree of crystallinity see Table 1.
In the table 1, the testing standard method of the silica alumina ratio Value Data of product beta zeolite is that icp analysis is (with reference to ZamechekW.Determination of the elemental compositor of zeolitic materials.In " VerifiedSyntheses of Zeolitic Materials ", Elsevier, 2001,51-53); Relative crystallinity all adopts industrial β 30 as estimating benchmarks, and the XRD spectra of said industrial β 30 samples is seen accompanying drawing 1, and the XRD spectra of the sample of embodiment 4 preparations is seen accompanying drawing 2, and the XRD spectra feature of embodiment 1-3 and 5 sample is with accompanying drawing 2.
Table 1
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 |
| The silicon source | Tetraethyl silicate | Tetraethyl silicate | Tetraethyl silicate | Methyl silicate | Methyl silicate |
| The aluminium source | Three aluminum ethylates | Three aluminum ethylates | Aluminum isopropylate | Aluminum isopropylate | Aluminum isopropylate |
| Hydrolytic reagent | Ammoniacal liquor | Nitric acid | Neutral ammonium fluoride | Neutral ammonium fluoride | Ammoniacal liquor |
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 |
| Each raw material consumption hydrofluoric acid, gram TEAOH, the cogelled quality of gram sial, gram particle degree, order | 3.421 33.06616.62620-40 | 4.104 39.66315.35940-60 | 4.275 41.33313.35040-60 | 4.082 39.679 11.559 100-200 | 4.446 42.986 12.691 100-200 |
| The crystallization temperature, ℃ time, day | 1603 | 1707 | 18010 | 17011 | 17020 |
| Raw material is formed, mol ratio SiO 2/Al 2O 3 Na 2O/SiO 2 TEA +/SiO 2 H 2O/SiO 2 F -/SiO 2 | 16 0.010.3 2.2 0.3 | 14 0.0050.4 2.1 0.4 | 12 - 0.52.50.5 | 10 - 0.61.50.6 | 7 - 0.651.5 0.65 |
| Product silica alumina ratio (SiO 2/Al 2O 3) | 19.2 | 18.6 | 17.3 | 15.5 | 10.8 |
| Relative crystallinity % | 85 | 100 | 105 | 114 | 40 |
Example 6～10
Raw material and the proportioning of embodiment 6～10 are shown in Table 2.It is cogelled at first to prepare sial, with the cogelled 12～48h that wear out under 20 ℃～220 ℃ of the sial of preparation, grinds to form then less than 20 order particles, and continues respectively to handle 24h down at 450 ℃, 550 ℃, 650 ℃, 860 ℃, 1150 ℃.Control suitable proportioning raw materials, add a certain amount of tetraethyl ammonium hydroxide, water and hydrofluoric acid, even through ultra-sonic dispersion or mechanical stirring.Be placed on then and carry out crystallization in the reactor, after reacted material washs after filtration, be drying to obtain aluminum-enriched beta zeolite at 120 ℃.
The XRD spectra feature of the sample of embodiment 6-10 is with accompanying drawing 2.
Table 2
| Embodiment | 6 | 7 | 8 | 9 | 10 |
| The silicon source | Tetraethyl silicate | Tetraethyl silicate | Methyl silicate | Tetraethyl silicate | Tetraethyl silicate |
| The aluminium source | Three aluminum ethylates | Aluminum isopropylate | Three aluminum ethylates | Aluminum isopropylate | Aluminum isopropylate |
| Hydrolytic reagent | Acetate | Hydrochloric acid | Ammoniacal liquor | Neutral ammonium fluoride | Ammoniacal liquor |
| Each raw material consumption hydrofluoric acid, gram TEAOH, the cogelled quality of gram sial, gram particle degree, order | 3.562 34.445 14.935 20～40 | 4.752 45.910 4.88 40～60 | 4.755 45.926 11.688 40～60 | 4.536 44.088 9.251 100～200 | 4.941 47.763 7.432 100～200 |
| The crystallization temperature, ℃ the time ask, day | 150 5 | 170 5 | 190 7 | 170 12 | 170 20 |
| Embodiment | 6 | 7 | 8 | 9 | 10 |
| Raw material is formed, mol ratio SiO 2/Al 2O 3 Na 2O/SiO 2 TEA +/SiO 2 H 2O/SiO 2 F -/SiO 2 | 15 0.01 0.3 2.5 0.3 | 14 - 0.4 2.5 0.4 | 10 - 0.5 2.5 0.5 | 6 - 0.6 2 0.6 | 3 - 0.65 2 0.65 |
| Product silica alumina ratio (SiO 2/Al 2O 3) | 19.0 | 18.2 | 15.9 | 9.6 | / |
| Relative crystallinity, % | 112 | 109 | 102 | 90 | 30 |
Adopt the aluminum-enriched beta zeolite of method provided by the invention preparation, its XRD spectra is compared with standard industry agent β 30, does not contain his stray crystal of tool equally.
Claims (10)
1. the preparation method of an aluminum-enriched beta zeolite is characterized in that this method contains following step:
(a) silicon source and aluminium source are mixed in the presence of hydrolytic reagent to obtain sial cogelled, said hydrolytic reagent is selected from one or more in the following material: organic acid, mineral acid, organic amine, ammoniacal liquor, Neutral ammonium fluoride;
(b) sial is cogelled through pulverizing as silicon and aluminum source after 20～220 ℃ of aging and 300～1400 ℃ of roastings;
(c) silicon and aluminum source is added in the solution of being made up of tetraethylammonium cation, ammonium radical ion, fluorion and water, forming the mole proportioning is SiO
2/ Al
2O
3=3～20, Na
2O/SiO
2=0～0.01, H
2O/SiO
2=1.0～8.0, TEA
+/ SiO
2=0.1～1.0, F
-/ SiO
2=0.1～1.0 reaction mixture;
(d) with reaction mixture crystallization and reclaim crystallization product in enclosed system.
2. according to the method for claim 1, said silicon source is dissolved in alcohol, facile hydrolysis.
3. according to the method for claim 2, said silicon source is tetraethyl silicate or methyl silicate.
4. according to the method for claim 1, said aluminium source is inorganic aluminate soluble in water or is the aluminium-alcohol salt that is soluble in alcohol.
5. according to the method for claim 4, said inorganic aluminate is selected from aluminum nitrate, Tai-Ace S 150 or aluminum chloride, and said aluminium-alcohol salt is aluminum isopropylate or trimethyl carbinol aluminium.
6. according to the method for claim 1, said sial is cogelled in the step (a), and it becomes the glue temperature to be controlled at 15～150 ℃, gelation time 5min～24h, and the pH value is controlled at 3～14.
7. according to the method for claim 6,25～80 ℃ of said one-tenth glue temperature, gelation time 10min～2h, pH value 6～13.
8. according to the process of claim 1 wherein that said organic acid is selected from formic acid, acetate or oxalic acid.
9. according to the process of claim 1 wherein that said mineral acid is nitric acid or hydrochloric acid.
10. according to the method for claim 7, said pH is 6～9.
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| JP4904417B2 (en) * | 2009-07-27 | 2012-03-28 | 日本化学工業株式会社 | Beta-type zeolite and method for producing the same |
| DE102010053054A1 (en) * | 2010-12-01 | 2012-06-06 | Süd-Chemie AG | Mechanochemical production of zeolites |
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| CN105621439B (en) * | 2014-10-30 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of synthetic method of Beta zeolites |
| CN105621438B (en) * | 2014-10-30 | 2017-08-11 | 中国石油化工股份有限公司 | A kind of rich aluminium Beta zeolite synthetic methods |
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| CN109133087A (en) * | 2017-06-27 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of synthetic method of Beta molecular sieve |
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| CN110540214B (en) * | 2018-05-28 | 2021-02-09 | 中国石油化工股份有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
| CN110856819B (en) * | 2018-08-24 | 2022-07-26 | 国家能源投资集团有限责任公司 | Surface aluminum-rich molecular sieve, preparation method and application thereof, isomerization reaction catalyst and application thereof |
| CN109516471B (en) * | 2018-12-24 | 2021-11-05 | 大连理工大学 | Synthesis method of ZSM-23 molecular sieve with aluminum-rich surface |
| CN112892472A (en) * | 2021-02-01 | 2021-06-04 | 中国科学院生态环境研究中心 | Beta molecular sieve adsorbent and preparation method and application thereof |
| CN113785751B (en) * | 2021-09-07 | 2023-06-20 | 广东百林生态科技股份有限公司 | Bougainvillea spectabilis culture medium and preparation method thereof |
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